Modified flame retardant polyphenylene ether resins having improved foamability and molded articles made therefrom

ABSTRACT

Polyphenylene ether compositions rendered flame retardant with bromine-containing compounds can be foam molded into shaped articles free of streaking and without the generation of odors if the foaming agent comprises citric acid and sodium bicarbonate.

This is a division of application Ser. No. 062,891 filed June 16, 1987now U.S. Pat. No. 4,728,675 which is a division of application Ser. No.900,705 filed Aug. 27, 1986 now U.S. Pat. No. 4,695,594.

FIELD OF THE INVENTION

The present invention relates to modified flame retardant polyphenyleneether resins having improved foamability. Such improvements are broughtabout by incorporating into a flame retardant polyphenylene ether resinan effective amount of a foaming agent comprising citric acid and sodiumbicarbonate. The invention also relates to foamed articles especiallylarge, high shot weight, low shot time articles, made from the modifiedpolyphenylene ether resins. As a result of the present invention,polyphenylene ether resin compositions produce foamed articles havingreduced surface streaking with no odor generation.

BACKGROUND OF THE INVENTION

Polyphenylene ether resins are high performance engineeringthermoplastics having relatively high melt viscosities and softeningpoints (i.e., in excess of 250° C.). They are useful for many commercialapplications requiring high temperature resistance and can be formedinto films, fibers and molded articles. For example, they can be used toform a wide range of products including household appliances, automotiveparts and trim. The polyphenylene ether resins and methods of theirpreparation have been thoroughly described in the patent literature,including Hay, U.S. Pat. Nos. 3,306,874 and 3,306,875 and Stamatoff,U.S. Pat. Nos. 3,257,357 and 3,257,358, and elsewhere.

As is well established, the polyphenylene ether resins may be utilizedalone or in admixture with styrene polymers over a broad spectrum ofproportions. The resulting blends can be molded into many of the samearticles made from polyphenylene ether resins alone, but with theadvantage that the moldings often possess better physical and/orchemical properties. Compositions of polyphenylene ether resins andstyrene polymers are also described in the patent literature, includingCizek, U.S. Pat. No. 3,383,435, and other patents known to those skilledin the art.

Compositions of polyphenylene ether resin and styrene polymers are notnormally flame retardant, and there are instances when it is desirableto impart a degree of flame retardancy to the compositions such that themolded articles are better able to resist burning or melting whenexposed to elevated temperatures or placed near an open flame. To thisend, it haas been disclosed in the art that certain halogenatedcompounds, and brominated compounds in particular, are effective asflame retardant additives for polyphenylene ether-polystyrene blends. Anexample of such a disclosure is Reinhard, U.S. Pat. No. 3,809,729.

Foamable compositions of polyphenylene ether resins with or withoutstyrene polymers are particularly suited as sources of lightweightstructural substitutes for metals, especially in the automotiveindustry.

Foaming agents are customarily employed to make moldable compositionsincluding compositions containing polyphenylene ether resins. Foamingagents tend to reduce the weight of a thermoplastic composition toachieve light weight properties by decomposing under reaction conditionswith the evolution of gas. Blowing agents have been used to obtainfoamable compositions of a variety of thermoplastic materials asdescribed in, for example, Muller et al., U.S. Pat. No. 3,781,233 andFox, U.S. Pat. No. 4,280,005 and the U.S. and British patent referencescited therein. Lundberg, U.S. Pat. No. 3,947,387 and Liu, U.S. Pat. No.4,588,754 disclose foamed polymeric products using citric acid, alone,or citric acid mixed with sodium bicarbonate as foaming agents.

Halogenated flame retardants (e.g. brominated styrene) are preferredover phosphate based flame retardants because the former exhibit lessstress cracking. However, previous attempts to incorporate halogenatedflame retardants into polyphenylene ether/polystyrene resins and then tofoam such compositions have not been successful because the compositionstend to degrade, often giving streaked articles, and generating odors,despite efforts to use a variety of foaming agents. This is especially aproblem when attempting to produce large sized articles by foaming thehigh shot weights (e.g., 14-16 oz. per part) and low shot times (e.g.,0.2 to 0.3 seconds per part).

Applicants have now discovered that a foaming agent comprising acombination of citric acid and sodium bicarbonate provides an effectivemeans of making moldable compositions derived from polyphenylene etherresins, styrene polymers and halogenated flame retardants (e.g.,brominated styrenes) without the evolution of undesirable by-productswhich lead to the decomposition of the moldable composition (e.g.surface streaking and odor generation). Moreover, the composition isuniquely suitable to produce large size foamed, shaped articles free ofstreaking and odor generation.

It is therefore an object of the invention to provide moldable, foamableflame retardant polyphenylene ether compositions with reduced surfacestreaking and odor generation.

It is still a further object of the invention to provide methods ofmaking and using such flame retardant polyphenylene ether compositions.

It is a principal object of the present invention to produce large sizedarticles by foaming flame retardant polyphenylene ether resincompositions using high shot weights and short shot times.

SUMMARY OF THE INVENTION

According to the present invention, there is provided a compositionadapted to the production of a flame retardant thermoplastic foamwithout surface streaking and odor generation, the compositioncomprising:

(a) a polyphenylene ether resin, alone, or combined with a styreneresin, especially a high impact polystyrene;

(b) an effective flame retardant amount of a halogenated flameretardant, alone, or in combination with an antimony compound,preferably a brominated polystyrene and most preferably a flameretardant additive of the formula: ##STR1## wherein x is about 2.8 and,preferably a brominated polystyrene combined with antimony oxide; and

(c) an effective foam generating amount of a foaming agent comprisingcitric acid and sodium bicarbonate.

The present invention also provides a method of improving resistance todecomposition of a foamable composition containing polyphenylene etherand a halogenated flame retardant compound.

In preferred features, the polyphenylene ether resin will comprisepoly(2,6-dimethyl-1,4-phenylene ether) and copolymers thereof. Thepreferred flame retardant agents are brominated polystyrenes asdescribed above. The foaming agent comprises a mixture of citric acidand sodium bicarbonate in an amount of 10 to 90% of citric acid and,correspondingly, 90 to 10% of sodium bicarbonate. Overall, the citricacid preferably comprises 0.25 to 1.0% and the sodium bicarbonatecomprises from 0.15 to 0.35% based on the total weight of thecomposition.

DETAILED DESCRIPTION OF THE INVENTION

The polyphenylene ethers (also known as polyphenylene oxides) used inthe present invention are a well known class of polymers which havebecome very useful commercially as a result of the discovery by Allan S.Hay of an efficient and economical method of production (See, forexample, U.S. Pat. Nos. 3,306,874 and 3,306,875). Numerous modificationsand variations have since been developed but, in general, they arecharacterized as a class by the presence of arylenoxy structural units.The present invention includes all such variations and modifications,including but not limited to those described hereninafter.

The polyphenylene ethers favored for use in the practice of thisinvention generally contain structural units of the following formula##STR2## in which in each of these units independently each Q¹ ishydrogen, halogen, primary or secondary lower alkyl (i.e., alkylcontaining up to 7 carbon atoms), phenyl, haloalkyl or aminoalkylwherein at least two carbon atoms separate the halogen or nitrogen atomfrom the benzene ring, hydrocarbonoxy, or halohydrocarbonoxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; and eachQ² is independently hydrogen, halogen, primary or secondary lower alkyl,phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined forQ¹. Examples of suitable primary lower alkyl groups are methyl, ethyl,n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl,2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl and the corresponding heptylgroups. Examples of secondary lower alkyl groups are isopropyl,sec-butyl and 3-pentyl. Preferably, any alkyl radicals are straightchain rather than branched. Most often, each Q¹ is alkyl or phenyl,especially C₁₋₄ alkyl, and each Q² is hydrogen.

Both homopolymers and copolymers are included. Suitable homopolymers arethose containing, for example, 2,6-dimethyl-1,4-phenylene ether units.Suitable copolymers include random copolymers containing such units incombination with, for example, 2,3,6-trimethyl-1,4-phenylene etherunits. Many suitable random copolymers, as well as homopolymers, aredisclosed in the patent literature, including the Hay patents mentionedabove and others. Also contemplated are graft copolymers, includingthose prepared by grafting onto the polyphenylene ether chain such vinylmonomers as acrylonitrile and vinyl aromatic compounds (for example,styrene), and such polymers as polystyrenes and elastomers. Still othersuitable polyphenylene ethers are the coupled polyphenylene ethers inwhich the coupling agent is reacted with the hydroxy groups of the twopolyphenylene ether chains to increase the molecular weight of thepolymer. Illustrative of the coupling agents are low molecular weightpolycarbonates, quinones, heterocyclic compounds and formals.

The polyphenylene ether generally has a molecular weight (numberaverage, as determined by gel permeation chromatography, whenever usedherein) within the range of about 5,000 to 40,000. The intrinsicviscosity of the polymer is usually in the range of about 0.4 to 0.5deciliters per gram (dl./g.), as measured in solution in chloroform at25° C.

The polyphenylene ethers may be prepared by known methods, and typicallyby the oxidative coupling of at least one correspondingmonohydroxyaromatic (e.g., phenolic) compound. A particularly useful andreadily available monohydroxyaromatic compound is 2,6-xylenol (in whichfor the above formula each Q¹ is methyl and each Q² is hydrogen), thecorresponding polymer of which may be characterized as apoly(2,6-dimethyl-1,4-phenylene ether).

Any of the various catalyst systems known in the art to be useful forthe preparation of polyphenylene ethers can be used in preparing thoseemployed in this invention. For the most part, they contain at least oneheavy metal compound, such as a copper, manganese or cobalt compound,usually in combination with various other materials.

Among the preferred catalyst systems are those containing copper. Suchcatalysts are disclosed, for example, in the aformentioned Hay U.S. Pat.Nos. 3,306,874 and 3,306,875, and elsewhere. They are usuallycombinations of cuprous or cupric ions, halide ions (i.e., chloride,bromide or iodide), and at least one amine.

Also preferred are catalyst systems containing manganese. They aregenerally alkaline systems containing divalent manganese and such anionsas halide, alkoxide or phenoxide. Most often, the manganese is presentas a complex with one or more complexing and/or chelating agents such asdialkylamines, alkanolamines, alkylenediamines, o-hydroxyaromaticaldehydes, o-hydroxyazo compounds, alpha-hydroxyoximes (both monomericand polymeric), o-hydroxyaryl oximes, and alpha-diketones. Also usefulare cobalt-containing catalyst systems. Those skilled in the art will befamiliar with patents disclosing manganese and cobalt-containingcatalyst systems for polyphenylene ether preparation.

Especially useful polyphenylene ethers for the purposes of thisinvention are those which comprise molecules having at least one of theend groups of formulas II and III, below, in which Q¹ and Q² are aspreviously defined, each R¹ is independently hydrogen or alkyl,providing that the total number of carbon atoms in both R¹ radicals is 6or less, and each R² is independently hydrogen or a C₁₋₆ primary alkylradical. Preferably, each R¹ is hydrogen and each R² is alkyl,especially methyl or n-butyl. ##STR3##

Polymers containing the aminoalkyl-substituted end groups of formula IImay be obtained by incorporating an appropriate primary or secondarymonoamine as one of the constituents of the oxidative coupling reactionmixture, especially when a copper- or manganese-containing catalyst isused. Such amines, especially the dialkylamines and preferablydi-n-butylamine and dimethylamine, frequently become chemically bound tothe polyphenylene ether, most often by replacing one of thealpha-hydrogen atoms on one or more Q¹ radicals adjacent to the hydroxygroup on the terminal unit of the polymer chain. During furtherprocessing and/or blending, the aminoalkylsubstituted end groups mayundergo various reactions, probably involving a quinone methide-typeintermediate of formula IV, below (R¹ is defined as above), withbeneficial effects often including an increase in impact strength andcompatibilization with other blend components. ##STR4##

Polymers with biphenol end groups of formula III are typically obtainedfrom reaction mixtures in which a by-product diphenoquinone of formulaV, below, is present, especially in a copper-halide-secondary ortertiary amine system. In this regard, the disclosures of the U.S. Pat.Nos. 4,234,706, 4,477,649 and 4,482,697 are particularly pertinent, andare incorporated herein by reference. In mixtures of this type, thediphenoquinone is ultimately incorporated into the polymer insubstantial amounts, chiefly as an end group. ##STR5##

In many polyphenylene ethers obtained under the conditions describedabove, a substantial proportion of the polymer molecules, usually asmuch as about 90% by weight of the polymer, contain end groups havingone or frequently both of formulas II and III. It should be understood,however, that other end groups may be present and that the invention inits broadest sense may not be dependent on the molecular structures ofthe polyphenylene ether end groups.

It will thus be apparent to those skilled in the art that a wide rangeof polymeric materials encompassing the full recognized class ofpolyphenylene ether resins are contemplated as suitable for use in thepractice of the present invention.

In the embodiments disclosed herein, compositions of polyphenyleneethers when combined with styrene resins can be made following theteachings in Cizek, U.S. Pat. No. 3,383,435. Although the blends canvary from 1 to 99 to 99 to 1, particularly preferred compositionscomprise from 25 to 75 parts by weight of a polyphenylene ether incombination with 75 to 25 parts by weight of a styrene resin.

The styrene resins, e.g., the rubber modified, polystyrenes which mayoptionally be used in the present composition may be selected from anyof the materials known generally in the art, including high impactpolystyrenes, or HIPS. In general, these modified polystyrene resins aremade by adding rubber during or after polymerization of the styrene, toyield an interpolymer of rubber and polystyrene, a physical admixture ofrubber and polystyrene, or both, depending on the particular processemployed.

Suitable rubber modifiers include polybutadiene, polyisoprene,polychloroprene, ethylene-propylene copolymers (EPR),ethylene-propylene-diene (EPDM) rubbers, styrene-butadiene-copolymers(SBR), and polyacrylates. The amount of rubber employed will vary,depending on such factors as the process of manufacture and individualrequirements.

Included within this family of materials for purposes of the presentinvention are more recently developed forms in which such factors as therubber particle size, the gel and cis contents of the rubber phase, andthe rubber volume percent are regulated or controlled to achieveimprovements in the impact resistance and other properties. These kindsof HIPS are described in the patent literature, including U.S. Pat. No.4,128,602 (Abolins, Katchman and Lee, Jr.), and U.S. Pat. No. 4,528,327(Cooper and Katchman), which are incorporated herein by reference.

Also contemplated as suitable for use are high impact polystyreneshaving morphological forms which are sometimes referred to ascore-shell, comprising particles of rubber encapsulated polystyrenedispersed in a matrix of polystyrene resin. Examples of this type aredisclosed in U.S. Pat. No. 4,513,120 (Bennett, Jr. and Lee, Jr.), aswell as the above-mentioned U.S. Pat. No. 4,528,327.

Preferably the styrene resin is one having at least 25% by weight ofpolymer units derived from a compound having the formula ##STR6## whereR² is hydrogen, lower alkyl or halogen; Z is a member selected from theclass consisting of vinyl, hydrogen, chlorine and lower alkyl; and p is0 or a whole number of from 1 to 5. Examples include rubber modifiedpolystyrenes and styrene containing copolymers such as thestyrene-acrylonitrile copolymers (SAN), styrene-butadiene copolymers,styrene-acrylonitrilealpha-alkyl styrene copolymers,styrene-acrylonitrilebutadiene copolymers (ABS),polyalpha-methylstyrene, copolymers of ethyl vinyl benzene, divinylbenzene and the like. The most preferred styrene resins are the highimpact polystyrenes.

Halogenated compounds, especially brominated styrenes are known in theart as effective flame retardant agents. The brominated styrenes includemono-, di-, tri-, tetra- and pentabromo styrenes and mixtures thereof.Such compounds have the formula ##STR7## wherein n is 1 to 5, preferably2.5-3.5.

Methods of preparing brominated styrenes are known in the art andtypically involve hydrobromination of the vinyl group followed bybromination of the nuclear ring of the bromo ethyl group to form thedesired product as disclosed for example in Hornbaker et al. U.S. Pat.No. 4,279,808 and Jackisch, U.S. Pat. No. 4,423,262. A preferredbrominated flame retardant agent is one within the above formula whereinn is about 2.8.

The blowing agents used in this invention are citric acid/sodiumbicarbonate concentrate blowing agents. These are known blowing agentsand are available from many commercial sources including C. H.Boehringer Sohn under the tradename Hydrocerol. Especially preferred isHydrocerol Compound (citric acid/sodium bicarbonate). Special mention ismade of Hydrocerol CLM70 supplied by Henly and Company, New York, N.Y.This formulation contains a polyethylene wax binder and has about 70% byweight of active ingredients. The decomposition temperature range isgenerally from about 150° C. to about 210° C., and the sole gaseousdecomposition product is carbon dioxide. These are preferred becauseneither the gaseous nor the solid decomposition products havedeleterious effects on the thermoplastic polymers. Furthermore, unlikenumerous other blowing agents, these blowing agents do not need thepresence of nucleating agents or activators in order to achieveuniformity of cells, although it is preferred. Additionally, theseblowing agents produced foams having the most uniform, fine cellularstructure.

The foaming agent can be added as a solid powder, as a dispersion in aninert liquid or with a diluent such as silica or a neutral clay or as aconcentrate wherein a high concentration of the foaming agent is carriedin a carrier polymer such as, for example, polyethylene. The particlesize of the foaming agent is usually sufficiently small to facilitateuniform blending with the thermoplastic polymers and is generally lessthan about 50 microns. However, since many commercial foaming agents areavailable in aggregate form, the particular size of the aggregate willbe somewhat larger.

The amount of blowing agent dispersed in the thermoplastic is thatamount which is sufficient to provide a uniform, essentially closed cellfoam manifesting the desired weight reduction and other physicalproperties. The density of the foam is preferably in the range of about0.4 to 1.2 g/cc, more preferably from about 0.7 to 1.0 g/cc.

The amount of blowing agent used for the desired foam density willdepend on the particular blowing agent selected, on the amount of gasgenerated by it upon decomposition and will depend on the particularmelt blending and extrusion process selected because the efficiency ofthe blowing agent can be affected by the tendency of a particular meltextruder to allow gaseous products to escape from the extruder. Ingeneral, the amount will range from about 0.05 to about 1.5% by weightbased on the polymer, preferably from about 0.1 to about 0.8% by weight,based on the polymer, to provide a sufficient degree of foaming withoutyielding an undesirably low density or open pore structure.

As is conventional, a synergist, e.g., an antimony compound can be usedwith the flame retardant, and this is usually preferred. Antimony oxide,for example, reduces the total amount of flame retardant halogencompound needed.

In formulating the compositions in accordance with the presentinvention, amounts for the above-mentioned components of the compositionpreferably fall within certain ranges, as follows.

    ______________________________________                                        COMPONENTS         AMOUNT (Parts by Weight)                                   ______________________________________                                        (a) polyphenylene ether, alone                                                                       75 to 95                                                   or combined w/a styrene resin                                             (b) flame retardant    1 to 25                                                (c) citric acid/sodium bicarbonate                                                                   0.05 to 1.5                                            ______________________________________                                    

The specified amounts are based on 100 parts by weight total of (a), (b)and (c) combined.

The weight ratio of polyphenylene ether resin to any styrene resin canvary from 1 to 99 to, correspondingly, 99 to 1. Preferably it will be inthe range of 25 to 75 to, correspondingly, 75 to 25.

The present compositions can also be formulated to include otheringredients in addition to those just described. These may be selectedfrom among conventional materials commonly employed in polyphenyleneether resin blends. Examples are plasticizers, mold release agents, meltviscosity reducers, colorants, stabilizers, antioxidants, mineralfillers (for example, clay), glass reinforcements, titanium oxides,lubricants, fragrances and so forth. Conventional amounts varying, forexample, from less than 1 to greater than 50 percent by weight, per 100percent by weight of the total composition, may be utilized.

The compositions can also be modified to include impact strengthimproving amounts of polymeric impact improvers, such as rubberystyrenic block copolymers, for example, di- or triblock copolymers ofstyrene and butadiene or the hydrogenated derivatives, i.e., styrene andethylene/butylene, as well as core-shell polymers, e.g., polyacrylatecore/styrene shell interpolymers.

Generally, the structural foams of the present invention may be preparedby any of the known methods in the art. For example, the foams may beprepared by dry mixing the blowing agent and polymer composition, andthereafter melt blending the composition in an extruder. The foams maybe injection molded, extruded and the like to produce finished articlesto stock materials.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS

The invention is further illustrated in the description below, which isset forth to show a preferred or best embodiment.

EXAMPLE 1

A composition was prepared comprising a polyphenylene ether resin(intrinsic viscosity 0.40 dl./g.), a high impact rubber-modifiedpolystyrene resin, a polybrominated polystyrene flame retardant,antimony oxide flame retardant synergist, a plasticizer, an impactmodifier, a rubber modified polystyrene (Hoechst, HOSTASTAT, HS-1), zincsulfide and zinc oxide as stabilizers, titanium dioxide as a pigment anda citric acid/sodium bicarbonate based blowing agent system. Thecomposition was extrusion blended in a 30 mm extruder at a temperatureprofile of 350°-400°-450°-530°-530°-530°-530° F. and comminuted intomolding pellets. It was foam molded into workpieces using a Toshiba foaminjection molding machine at barrel temperatures of 400°-560°-560°-540°F. (profile) and mold temperature of 90° F. For comparison purposes,slabs were molded from identical compositions using a state-of-the-artblowing agent, a preblend of a 70/30 w/w combination of,azodicarbonamide and 5-phenyl-3,6-dihydro-1,3,4-oxadiazin-2one in aplasticized high impact polystyrene resin, 8% by weight activeingredients, using in this case, a Siemag molding machine and producing18"×6"×0.250" end gated panels, for testing. The formulations used andthe results obtained are set forth in Table 1:

                  TABLE 1                                                         ______________________________________                                        Foamed Flame Retardant Polyphenylene                                          Ether Compositions                                                            Example               1      1A*                                              ______________________________________                                        Composition (parts by weight)                                                 Poly(2,6-dimethyl-1,4-phenylene ether)                                                              50     50                                               Rubber Modified Polystyrene                                                                         50     50                                               (9% polybutadiene)                                                            Polybrominated Polystyrene.sup.a                                                                    9.5    9.5                                              Antimony Oxide        3.3    3.3                                              Butylene o-phthalate plasticizer                                                                    7.5    7.5                                              Styrene-ethylene butylene block                                                                     5      5                                                copolymer impact modifier.sup.b                                               Rubber modified polystyrene.sup.c                                                                   1      1                                                Zinc sulfide stabilizer                                                                             0.15   0.15                                             Zinc oxide stabilizer 0.15   0.15                                             Titanium dioxide pigment                                                                            5      5                                                Citric acid/sodium bicarbonate                                                                      1      --                                               blowing agent.sup.d, phr                                                      Azodicarbonamide/5-phenyl-3,6-dihydro-                                                              --     6                                                1,3,4-oxadiazine-2-one.sup.e                                                  Properties                                                                    Surface streaking     none   brown                                            Odor generation       none   substantial                                      ______________________________________                                         *Comparison                                                                   .sup.a Ferro Co. PC68PB                                                       .sup.b Shell Chemical Company Kraton G1652                                    .sup.c Hoechst Co., HOSTASTAT                                                 .sup.d Henly and Co., Hydrocerol CLM 70                                       .sup.e U.S. Pat. No. 4,097,425, Example 1, 8% active ingredients in           plasticized high impact rubber modified polystyrene                      

No discoloration was observed in Example 1 or other signs of resindecomposition when large parts were foam molded. The addition of thermalstabilizer, e.g., epoxidized soybean oil and/or dialkyl tin dimaleate tothe comparison formulation did not reduce the amount of decomposition.Moreover, the physical properties of the article of Example 1 werecomparable to those of the comparative example even though all of thepreviously described decomposition was eliminated and in spite of thefact that less foaming agent was required. The foam density was 0.90g./cc.

EXAMPLES 2-8

The present procedure of Example 1 was repeated making formulaadjustments and substituting other flame retardant agents as well asadding other ingredients. The compositions were foam molded and testedfor density, surface appearance and odor generation. The compositionsused and the results obtain are set forth in Table 2:

                                      TABLE 2                                     __________________________________________________________________________    Foamed Flame Retardant Polyphenylene                                          Ether Compositons                                                             Example         2  3  4  5  6  7  8                                           __________________________________________________________________________    Composition (parts by weight)                                                 Poly(2,6-dimethyl-1,4-phenylene                                                               50 50 50 50 50 50 50                                          ether                                                                         High-impact rubber modified                                                                   50 50 50 50 50 50 50                                          polystyrene (9% polybutadiene)                                                Polybrominated Polystyrene A.sup.a                                                            9.5                                                                              10 10 10 5.5                                                                              -- --                                          Polybrominated Polystyrene B.sup.b                                                            -- -- -- -- -- 9.5                                                                              10                                          Polybrominated bis-o-phthalate.sup.c                                                          -- -- -- -- 7.5                                                                              -- --                                          Antimony oxide  3.3                                                                              3.4                                                                              3.4                                                                              3.4                                                                              3.4                                                                              3.4                                                                              3.4                                         Butylene o-phthalate plasticizer.sup.d                                                        7.5                                                                              7.5                                                                              7.5                                                                              7.5                                                                              7.5                                                                              7.5                                                                              7.5                                         Styrene ethylene butylene                                                                     5.0                                                                              4.0                                                                              4.0                                                                              4.0                                                                              5.0                                                                              5.0                                                                              5.0                                         block copolymer.sup.e                                                         Rubber Modified Polystyrene.sup.f                                                             1.0                                                                              1.2                                                                              1.2                                                                              1.2                                                                              1.0                                                                              1.0                                                                              1.0                                         Zinc sulfide    0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                                        Zinc Oxide      0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                                        Titanium dioxide                                                                              5.0                                                                              -- -- -- 5.0                                                                              5.0                                                                              5.0                                         fumed silica.sup.g                                                                            -- -- 0.5                                                                              -- -- -- --                                          pigment.sup.h   -- -- 0.38                                                                             -- -- -- --                                          pigment.sup.i   -- -- 0.22                                                                             -- -- -- --                                          pigment.sup.j   -- -- 0.06                                                                             0.5                                                                              -- -- --                                          Fragrance.sup.k 0.3                                                                              -- 0.3                                                                              -- -- -- --                                          Citric acid/sodium bicarbonate                                                                1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                         blowing agent                                                                 Properties                                                                    Surface streaking                                                                             none                                                                             none                                                                             none                                                                             none                                                                             none                                                                             none                                                                             none                                        Odor generation none                                                                             none                                                                             none                                                                             none                                                                             none                                                                             none                                                                             none                                        __________________________________________________________________________     .sup.a Ferro Co. PC68PB                                                       .sup.b Great Lakes Co. CN348L                                                 .sup.c Pennwalt Co. FR40B                                                     .sup.d ADMEX 433B                                                             .sup.e Shell Co. KRATON G1652                                                 .sup.f Hoechst Co. HOSTASTAT                                                  .sup.g Cabot Co., Cabosil MF                                                  .sup.h No. 909                                                                .sup.i No. MMC 314                                                            .sup.j No. M 800                                                              .sup.k IFF Co. Green Apple                                               

The foamed articles exhibited no surface streaking or odor generation.

In addition to foam density measurements, other physical propertymeasurements and flammability tests were made on the articles of Example1, 6 and 8 and in state-of-the-art Comparative Example 1A. The resultsare set forth in Table 3:

                  TABLE 3                                                         ______________________________________                                        Physical and Flammability Properties                                          of Flame Retardant Polyphenylene Ether                                        Found Compositions                                                                          Example                                                         Properties      1A     1        (6)   (8)                                     ______________________________________                                        Flammability rating,                                                                          V-O    V-O(3)   V-O(2)                                                                              V-O(3)                                  Underwriters Laboratory                                                                       pass   pass     pass  pass                                    UL 94                                                                         Heat distortion temp.                                                                          180    187      193   188                                    @ 266 psi, °F.                                                         Melt viscosity, poise                                                                         1345   1326     1345  1249                                    Tensile yield, psi                                                                            3400   3775     4598  4264                                    Flexural modulus, kpsi                                                                         261    264      304   300                                    Flexural strength, psi                                                                        6800   6995     8075  7620                                    Ductile impact (Dynatup)                                                                       200    224      188   144                                    units                                                                         ______________________________________                                    

The foregoing tables demonstrate that the compositions according to thisinvention meet or exceed the properties exhibited by the state of theart composition. The parts also show improved processability in largepart from molding and improved surface in low pressure foam, andexcellent appearance in counter pressure foam. The use of certain flameretardants in combination, Example 6, can obviate the need to use aplasticizer. Other tests have shown that impact strength retention isexcellent even at the highest weight reductions. The addition offragrance, while unnecessary, does not adversely affect physicalproperties, even in thin walled forms when using the blowing agent ofthis invention. No decomposition was evident even when molding a 3.5pound part at a 0.8 second high shot speed.

When used herein and in the appended claims the terms "high shot weight"means in excess of about 0.5 pound per workppiece and the term "low shottime" or "high shot speed" means less than about 2 seconds/cycle.

The above-mentioned patents and publications are incorporated herein byreference.

Many variations of the present invention will be obvious to thoseskilled in this art in light of the above, detailed description. Forexample, instead of poly(2,6-dimethyl-1,4-phenylene ether) other resinscan be used, such as poly(2,6-dimethyl-co-2,3,6-trimethyl-1,4-phenyleneether). All such obvious variations are within the full intended scopeof the appended claims.

The rubber-modified styrene resin can be replaced by a styrenehomopolymer, or it can be omitted from the composition. The antimonyoxide can be replaced into other antimony compounds such as an antimonyester, or it can be omitted. Instead of a brominated polystyrene, achlorinated polystyrene can be used, or there can be substituted otherflame retardant compounds such as decabromodiphenyl ether.

I claim:
 1. A foamed shaped article having high tensile strength,substantially free of surface streaking and substantially free of odorgeneration produced by heating and foaming a composition comprising (a)a polyphenylene ether, alone, or in combination with a styrene resin;(b) an effective flame retarding amount of a halogenated flameretardant, alone, or in combination with an antimony oxide compound; and(c) an effective foam generating amount of a foaming agent comprisingcitric acid and sodium bicarbonate.
 2. A large foamed shaped articleaccording to claim 1, produced using a shot weight in excess of about0.5 pounds and a shot time of less than about 2 seconds per cycle.
 3. Anarticle according to claim 1 wherein component (a) is present in anamount of from 75 to 99 parts by weight, component (b) is present in anamount of 1 to 25 parts by weight and component (c) is present in anamount of 0.05 to 1.5 parts by weight per 100 parts by weight of (a),(b) and (c) combined.
 4. An article according to claim 1, whereinpolyphenylene ether resin (a) is a homopolymer or copolymer containingstructural units of the formula ##STR8## in which for each of theseunits independently each Q¹ is hydrogen, halogen, primary or secondarylower alkyl having up to seven carbon atoms, phenyl, haloalkyl oraminoalkyl wherein at least two carbon atoms separate the halogen ornitrogen atom from the benzene ring, hydrocarbonoxy, orhalohydrocarbonoxy wherein at least two carbon atoms separate thehalogen atom and oxygen atoms; and each Q² is independently hydrogen,halogen, primary or secondary lower alkyl, phenyl, haloalkyl,hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹.
 5. An articleaccording to claim 1, wherein the polyphenylene ether resin ispoly(2,6-dimethyl-1,4-phenyl ether).
 6. An article according to claim 5,wherein the poly(2,6-dimethyl-1,4-phenylene ether) has an intrinsicviscosity of about 0.4 to 0.5 deciliters per gram in chloroform at 25°C.
 7. An article according to claim 1, wherein polyphenylene ether resin(a) is poly(2,6-dimethyl-co-2,3,6-trimethyl-1,4-phenylene ether).
 8. Anarticle according to claim 1, wherein the styrene resin is a high impactrubber modified styrene resin.
 9. An article according to claim 1,wherein the foaming agent comprises 10 to 90% by weight of citric acidand, correspondingly, 90 to 10% by weight of sodium bicarbonate.
 10. Anarticle according to claim 1, wherein the halogenated flame retardant isa brominated styrene having the formula: ##STR9## wherein n is from 1 to5.
 11. An article according to claim 10 wherein n is about 2.8.
 12. Alarge foamed shaped article according to claim 2 wherein the shot weightis in the range of about 0.5 pounds to about 3.5 pounds.
 13. A largefoamed shaped article according to claim 2 wherein the shot weight isfrom about 14 to about 16 ounces.
 14. A large foamed shaped articleaccording to claim 2 wherein the shot time is less than about 0.8seconds.
 15. A large foamed shaped article according to claim 2 whereinthe shot time is in the range of about 0.2 to about 0.3 seconds.